Semiesters of unsaturated dicarboxylic acids



Patented Nov. 27, 1951 SEMIESTERS OF UNSATURATED DICARBOXYLIC ACIDS Otto Albrecht, Nenewelt, near Basel, Switzerland,

assignor to Ciba Limited, a Swiss firm No Drawing. Application August 20, 1948, Serial No. 45,438. In Switzerland April 9, 1945 14 Claims. (011252-215) This application is a continuation-in-part of my application Serial No. 655,364, filed March 18, 1946 (now abandoned).

The present invention relates to a water-soluble composition of matter producing a (softening effect on regenerated cellulose when applied in hard water which comprises (a) a water-soluble salt of a semi-ester obtainable by reacting 1 molecular proportion of an aliphatic compound having at least 12 carbon atoms and containing at least one alcoholic hydroxyl group, at least one hetero-atom interrupting the carbon chain, and being free from basic nitrogen atoms, with 1 molecular proportion of an unsaturated aliphatic or cycloaliphatic dicarboxylic acid or a functional derivative thereof, and (b) a lime-resistant dispersing agent, in which an aliphatic radical containing at least 12 carbon atoms is bound to a sulfonic acid group by a bridge containing at least one hetero atom. As aliphatic compounds having at least 12 carbon atoms and containing at least one allphatic hydroxyl group and at least one heteroatom interrupting the carbon chain, and free from basic nitrogen atoms, there may be used, for example, the following: N-hydroxyalkyl amides and hydroxyalkyl esters of higher fatty acids, such as N-(p-hydroxyethyl) -palmitic acid amide, N-(p-hydroxyethyl)-stearic acid amide,

' N-(p-hydroxyethyl)-oleic acid amide, N-(2-hydroxypropyl)-stearic acid amide; or stearic acid p-hydrcxyethyl ester; hydroxyalkyl ethers of higher fatty alcohols, such as octadecylalcoh'ol 'fi-hydroxyethyl ether; and also thio-ethersof high molecular weight containing hydroxyalkyl groups such as octadecyl-fl-hydroxyethyl thioether. These examples show that in this invention the compounds used'as startingmaterials may contain N, O or S as hetero-atoms. Products containing-N or O atoms as hetero-atoms are especially suited as starting materials for they are very easy to obtain. N and O atoms may be designated as hetero-atoms having an atomic weight of 14 to 16. N-hydroxy-alkylamides and hydroxyalkylesters, the hetero-atoms of which are N- or O-atoms, have a number of properties in common. They are neutral substances; are easily soluble in organic solvents; owing to their common OH-group they readily emulsify in water; and are saponifled by boiling with mineral acidsduring which operation fatty acids are formed.

Among the unsaturated aliphatic or cycloaliphatic dicarboxylic acids to be used as starting materials the following may be mentioned as examples: Ethylene-a:fl-dicarboxylic acids, that is to say fumaric acid or maleic acid; also cyclohexene dicarboxylic acids, for example, addition products of maleic acid with butadiene or its homologs, such as tetrahydrophthalic acid (the addition product of maleic acid with butadiene). As functional derivatives of these dicarboxylic acidsthere are especialy suitable their anhydrides.

The reaction of the hydroxyl compounds with the dicarboxylic acids may be carried out by heating a mixture of the starting materials, advantageously with the addition of a small quantity of a strong acid, until 1 molecular proportion of water has been split off. It is of advantage, however, to heat the hydroxyl compound with the dicarboxylic anhydride, for example, at C., until a test portion of the reaction mixture dissolves in a dilute solution of sodium hydroxide.

The semi-esters of the compositions of matter according to the present invention are soluble in water in the form of their alkali salts, or in the form of salts of Water-soluble amines or in the form of ammonium salts. and can be used as textile assistants. The alkali salts of the new semi-esters, owing to their capillary activity, can be used as foaming or cleansing agents. Special mention must be made of the soft feel which is imparted to cellulose fibers, especialy in hard water, by the salts of the semi-esters of the invention when they contain an aliphatic residue of at least 16 carbon atoms, preferably 16-18 carbon atoms. The alkali salts of the semi-esters are distinguished by an especially good solubility in neutral or weakly acid liquors used in the textile industry, especially in baths used to impart anti-creasing properties to textiles. Textiles which have been rendered anti-creasing with the addition of water-soluble salts of the semi-esters of this invention possess a soft and flowing feel. The composition of matter of the present invention, however, are even more effective, because they do not form precipitations in hard water.

The following substances are examples of limeresistant dispersing agents which may be contained in the compositions of matter of the present invention: water-soluble salts of sulfonated fatty alcohols or of sulfonated N-hydroxy-alkylamides of higher fatty acids or of aliphatic amino sulfonic acids, hydroxy sulfonic acids which are acylated at the amino or hydroxy group respectively by higher fatty acids; water-soluble salts of monoesters of higher fatty alcohols and 4-! sulfophthalic acid; water-soluble salts of sulfonated a-alkyl-benzimidazoles wherein the alkyl radical contains at least 11 carbon atoms such as the alkali metal salts of N-benzyl-pheptadecyl-benzimidazole disulfonic acid; watersoluble salts of condensation products of the formula RCONI-ICH2SCH2-CI-Ia-SO3H wherein R-CO is the acyl radical of a fatty acid containing at least 12 carbon atoms; Prodr,

ucts of the last named type are obtainable. by condensing N-methylolamides of fatty acids with fi-mercapto ethane sulfonic acid. The substances mentioned above are especially effective lime-resistant dispersing agents and are characterized. by the fact that an aliphatic radical containing at least 12 carbon atoms is bound to a sulfonic acid group by a bridge containing at least one hetero-atom. In the above examples the hetero atoms are nitrogen, oxygen or sulfur atoms.

The compositions of matter of the present invention may contain, for instance, about -50 per cent of a lime-resistant dispersing agent. Mixtures containing about -40 per cent of these dispersing agents are especially valuable.

Among the semi-esters used in the present in vention there are particularly easily obtained water-soluble salts, for instance alkali metal salt, ammonium salts and amine salts. of semi-esters of the formula is the acyl radical of a fatty acid containing at least 12 carbon atoms, 3: is a member selected from the group consisting of imino nitrogen "and oxygen, R1 alkylene, and R3 is unsaturated a k lene- The following formulae illustrate some of the groups of the products of this invention:

wherein R. R1 and R2 have the meaning. indicated above;

wherein R. and R1 have the meaning indicated above.

has the meaning given above;

0 o H H n-0 o-o= 0 o-cnrom-o 0 1 wherein has the meaning given above.

The following examples illustrate the invention, the parts being by weight:

Example 1 32.5 parts of N-(B-hydroxyethyl)-stearic acid amide and 9.8 parts of maleic anhydride are stirred at l00 C. until a test portion when neutralized with sodium hydroxide solution dissolvesin'water to give a clear solution. This is the case after about 3 hours. The resulting acid ester of maleic acid is then converted into its sodium salt by neutralization with sodium hy-. droxide or sodium carbonate, advantageously after being previously dissolved in ethyl alcohol. After being dried, the sodium salt of the new semi-ester of the formula represents the acyl radical of commercial Stearic aci is a app oximat ly colo less. powder, whi h, when. t ken p n w ter. form a cle r. foaming solution. It may be used as a textile assistant, f a pl as a. v ry ef e tive sbft nine a nt for cellulose fibers. Eorthis purpose, there is suitable, for example. a mixture of 70 parts of the aioresa d sod um'salt and 30 a s o t d sed m salt. of N-bemy -an ntad qvlz midazole disulfonic acid. Qctadecylesehydroxyethyle thioether or octadecyl-sehydroxyethylether or N-(p-hydr xypropyl)e tearic a d amide or he firli ydr xye hy emid of cccoanut. ia ty a i n al o be esterifi d n. h same. ma er i m ic acid. ESters of fumaric acidcan .be prepared by adding a small quantity of a stron acid to the mixture of the starting materials and heat? ing it until one molecular proportion of water is pl t I 7 Q I Instead of the disodium salt of the above benzimidaaole, disulfonic acid the sodium salt of the acid sulfuric acid ester of dodeoyl alcohol or of the monoc tvl es er. of u ep a d. r f B iN lfieyl-N meth bamin l th n. sulf acid or of the oleic acid ester of c-hydroxyethane- -sulfonic acid. or of the sulfonic acid of he form l attests being the acyl radical of commercial stearic acid) may be used.

Example 2 32.5 parts of N-(fi-hydroxyethyD-oleic acid amide and 9.8 parts of maleic anhydride are stirred at 95-100" C. until a test portion when neutralized with sodium hydroxide solution gives a clear solution in water. This is the case after a few hours. The resulting semi-ester of :maleic Example 3 6.3 parts of stearic acid B-hydroxyethyl ester" and 2.1 parts of maleic anhydride are heated,

while stirring, at 95-100 C. for about 3 hours, the esterification mixture is dissolved in ethyl alcohol, neutralized with dilute sodium hydroxide solution, and the whole is evaporated to dryness. The new sodium salt of a compound of the formula represents the acyl radical of commercial stearic acid, so obtained, which can be freed from small quantities of a by-product-by extraction with acetone, is an approximately colorless mass, which dissolves in warm water to form a foaming solution. It can be used as a textile assistant, for example, as a softening agent, especially in admixture with the lime-resistant dispersing agents as mentioned in Example 1. Mixtures of this type may contain 20-30 per cent. of the lime resistant dispersing agent.

The ,B-hydroxyethyl ester of oleic acid or of cocoanut fatty acid can be prepared in a similar manner.

Example 4 Viscose rayon yarn is softened in the following manner: 0.015 part of the mixture described in Example 1 is dissolved in 300 parts of water of 20 German hardness, and parts of viscose rayon yarn are treated with the solution at 30 C. for 30 minutes. After centrifuging and dry-' ing, the yarn so treated has a very soft and smooth feel.

What I claim is:

1. A water-soluble composition of matter producing a softening effect on regenerated cellulose when-applied in hard water; consisting essentially of"(a) 50 to of a water-soluble salt of a wherein is the acyl radical of a fatty acid containing at least 12 carbon atoms, a: is a member selected from the group consisting of imino nitrogen and oxygen, R1 is alkylene and R2 is unsaturated alkylene, and (b) 10 to 50% of a lime-resistant dispersing agent, in which an aliphatic radical containing at least 12 carbon atoms is bound to a sulfonic acid group by a bridge containing at least one hetero atom, said agent being selected from the group consisting of sulfonated -alkylbenzimidazoles wherein the ,u-alkyl radical contains at least 12 carbon atoms, acid sulfuric acid esters of fatty alcohols containing at least 12 carbon atoms, aliphatic amino sulfonic acids wherein the amino group is acylated by a fatty acid containing at least 12 carbon atoms, aliphatic hydroxy sulfonic acids wherein the hydroxy group is acylated by a fatty acid containing at least 12 carbon atoms, and mono-esters of fatty alcohols containing at least 12 carbon atoms with aromatic dicarboxylic monosulfonic acids of the benzene series.

2. A water-soluble composition of matter producing a softening effect on regenerated cellulose when applied in hard water, consisting essentially of (a) 50 to 90% of a water-soluble salt of a semi-ester of an unsaturated aliphatic dicarboxylic acid of the formula 0 0 /0 -c o-R,(J

N-m-o on is the acyl radical of a fatty acid containing at least 12 carbon atoms. R1 is alkylene and R2 is unsaturated alkylene, and (b) 10 to 50% of a lime-resistant dispersing agent, in which an aliphatic radical containingat least 12 carbon atoms is bound to a sulfonic acid group by a bridge containing at least one hetero atom, said agent being selected from the group consisting of sulfonated i-alkyl-benzimidazoles wherein the ,u-alkyl radical contains at least 12 carbon atoms, acid sulfuric acid esters of fatty alcohols containing at least 12 carbon atoms, aliphatic amino sulfonic acids wherein the amino group is acylatedby a fatty acid containing at least 12 carbon atoms, aliphatic hydroxy sulfonic acids wherein the hydroxy group is acylated by a fatty acid containing at least 12 carbon atoms, and monoesters of fatty alcohols containing at least 12 carbon atoms with aromatic dicarboxylic monosulfonic acids of the benzene series. 1

3. A water-soluble composition of matter producing a softening effect on regenerated cellulose when applied in hard water, consisting .fe'ssentially of -(a) 50 to 90% of a water-soluble isthe acyl radical of a fatty acid containing at least 12 carbon atoms, and R1 is alkylene, and (b) 10- to 50% of a lime-resistant dispersing agent, in which an aliphatic radical containing at least 12 carbon atoms is bound to a sulfonic acid group by a bridge containing at least one hetero atom, said agent being selected from the group consisting of sulfonated ,u-allcyl-benzimidazoles wherein the -alkyl radical contains at least 12 carbon atoms, acid sulfuric acid esters of fatty alcohols containing at least 12 carbon atoms, aliphatic amino sulfonic acids wherein the amino group is acylated by a fatty acid containing at least 12 carbon atoms, aliphatic hydroxy sulfonic acids wherein the hydroxy group is acylated by a fatty acid containing at least 12 carbon atoms, and mono-esters of fatty alcohols containing at least 12 carbon atoms with aromatic'dicarboxylic monosulfonic acids of the benzene series.

4. A water-soluble composition ofmatter producing a softeningefiect on regenerated cellulose'when applied in hard water, consistingessentially of (a) 50 to 90% of a water-soluble salt of a semi-ester of an unsaturated aliphatic dicarboxylic acid of the formula is the acyl radical of a fatty acid containing- 16-18, carbon atoms, and R; is alkylene, and (b)v 10 to, 50% of a lime-resistant dispersing agent, in

said agent being selected from the group consisting of carbon, atoms, acid sulfuric acid esters of fatty alcohols. containing at least 12 carbon, atoms,

aliphatic amino sulfonic acids wherein theamino group is acylated by a fatty acid containing at. least 12 carbon atoms, aliphatic hydroxy sulfonic,

acids wherein the hydroxy group, isacylated; by

,a fatty acidcontaining at least 12 carbon atoms, and monoesters of fatty alcohols containing; at

least 12 carbon atoms with aromatic dicarboxylic monosulfonic acids of the benzene series,

5 A water-soluble composition: of matter procin a o ni efiect e ener e el? w e pplied in hard Waten c nsis i g n scan ily of (a), .0 b91909? of a waterzsolubier lul sulfonated -alkyl-benzimidazoles. wherein the, i-alkyl radical contains at least: 12,

a 0. a emi-ester of a unsaturated aliphatic dicarboxylic acid of the formula is the acyl radical of a fatty acid containing 16 to 18 carbon atoms, and (b) 10 to 50% of a lime taining at least one hetero atom, said agent being selected from the group consisting of sulfonated -alkyl-benzimidazoles wherein the alkyl radical contains at least 12 carbon atoms, acid sulfuric acid esters of fatty alcohols containing at least 12 carbon atoms, aliphatic amino sulfonic acids wherein the amino, group is acylat ed by a fatty acid containing at least 12 carbon atoms, aliphatic hydroxy sulfonic acids wherein the hydroxy group is acylated by a fatty acid containing at least 12 carbon atoms, and monoesters of fatty alcohols containing at least 12 carbon atoms with aromatic. dicarbcxylic monosulfonic acids of the benzene series.

6. A water-soluble composition of matter producing a softening effect. on regenerated cellulose when applied in hard water, consisting essentially of (a) 50 to of a water-soluble salt of a semi-ester of an unsaturated aliphatic dicarboxylic acid of the formula is the, acyl radi al of commercial stearic acidand (b) 10 to 50% of a lime-resistant dispersing agent, in which an aliphatic radical containing atleast 12 carbon atoms is bound to a, sulfonic acid group by abridge containing at least one hetero atom, said agentbeing selected from the group consisting of, sulfonated, -alkyl-benzimidazoles wherein the l .'1ky1'1 aJd.iQaf 1- contains at least 12 carbon atoms, acid sulfuric acid esters.

dicarboxylic, monosulfonic acids, of the. benzene,

series. a

7. A water-soluble composition ofmatter producing, a softening effect on: regenerated, cellulOSQWhen, applied in hardy water, consisting es-.1 sentially of (a), 59 1p 90%,- of, a Water-soluble.

.-. 9 salt of a semi-ester of an unsaturated aliphatic dicarboxylic acid of the formula is the acyl radical of commercial stearic acid and (b) 10 to 50% of an alkali salt of a sulfonated -alkyl-benzimidaaole wherein the ,ualkyl radical contains at least 11 carbon atoms. 1 8. A water-soluble composition of matter producing a softening effect on' regenerated cellulose when applied in hard water, consisting es sentially of (a) 50 to 90% of a water-soluble salt of a semi-ester of an unsaturated-aliphatic di carboxylic acid of the formula is the acyl radical of commercial stearic acid, and (b) 10 to 50% of an alkali salt of N-benzylheptadecyl-benzimidazole-disulfonic acid.

9. A water-soluble composition of matter producing a softening effect on regenerated cellulose when applied in hard water, consisting essentially of (a) 50 to 90% of a water-soluble salt of a semi-ester of an unsaturated aliphatic dicarboxylic acid of the formula is the acyl radical of commercial oleic acid and (b) 10 to 50% of a lime-resistant dispersing agent, in which an aliphatic radical containing at least 12 carbon atoms is bound to a sulfonic acid group by a bridge containing at least one hetero atom, said agent being selected from the group consisting of sulfonated -alkyl-benzimidazoles wherein the a-alkyl radical contains at least 12 carbon atoms, acid sulfuric acid esters of fatty alcohols containing at least 12 carbon atoms, aliphatic amino sulfonic acids wherein the amino group is acylated by .a fatty acid containing at least 12 carbon atoms, aliphatic hydroxy sulfonic acids wherein the hydroxy group is acylated by a fatty acid containing at least 12 carbon atoms, and mono-esters of fatty alcohols containing at least 12 carbon atoms with aromatic dicarboxylic monosulfonic acids of the benzeneseries.

10. A water-soluble composition of matter producing a softening effect on regenerated cellulose when applied in hard water, consisting essentially of (a) 50 to 90% of a water-soluble salt of a 10 semi-ester of an unsaturated aliphatic dicarboxylic acid of the formula 1 is the acyl radical of commercial oleic acid, and (b) 10 to 50% of an alkali salt of a sulfonated r-alkyl-benzimidazole wherein the -alkyl radical contains at least 11 carbon atoms. 2

11. A water-soluble composition of matter producing a softening effect on regenerated cellulose when applied in hard water, consistingessentially of (a) 50 to of a water-soluble salt of a semi-ester of an unsaturated aliphatic dicar boxylic acid of the formula is the acyl radical of commercial oleic acid and (b) 10 to 50% of an alkali salt of N-benzyl-pheptadecyl-benzimidazole disulfonic acid.

12. A water-soluble composition of matter producing a softening effect on regenerated cellulose when applied in hard water, consisting essentially of (a) 50 to 90% of a water-soluble salt of a semi-ester of an unsaturated aliphatic dicarboxylic acid of the formula is the acyl radical of commercial stearic acid and (b) 10 to 50% of a lime-resistant dispersing agent, in which an aliphatic radical containing at least 12 carbon atoms is bound to a sulfonic acid group by a bridge containing at least one hetero atom, said agent being selected from the group consisting of sulfonated -alkyl-benzimidazoles wherein the -radical contains at least 12 carbon atoms, acid sulfuric acid esters of fatty alcohols containing at least 12 carbon atoms, aliphatic amino sulfonic acids wherein the amino group is acylated by a fatty acid containing at least 12 carbon atoms, aliphatic hydroxy sulfonic acids wherein the hydroxy group is acylated by a fatty acid containing at least 12 carbon atoms, and monoesters of fatty alcohols containing at least 12 carbon atoms with aromatic dicarboxylic monosulfonic acids of the benzene series.

13. A water-soluble composition of matter producing a softening effect on regenerated cellulose when applied in hard water, consisting essentially of (a) 50 to 90% of a water-soluble salt of a asmsee 12 semi-ester or an unsaturated aliphatic dicarwherein boxylic acid of the formula o H H R-C 2' 0 5 v l "Q K is the acyl radical of commercial stearic acid,

'O-CHr-CHz-O- J f0 and (b) to 50% of an alkali salt of N-benzyl- -heptadecyl-benzimidazole disulfonic acid. OTTO ALBRECHT, wherein 0 10 REFERENCES CITED The following references are of record in the file of this patent:

the acyl radical of commercial stearic acid and UNITED STATES PATENTS \(b) 1.0 to 50% 01 an alkali San; of a .sulfonated Number Name Date -alkyl-benzimidazole wherein the -alkyl radical 2,023,976 Roberts Dec. 10, 1935' contains at least 11 carbon atoms. 2,036,525 Granacher Apr. 7, 1936 14. A water-soluble composition of matter pro- 2,043,164 Granacher ,V.-,... June 2, 19 36 duping a softening effect on regenerated cellulose 2,069,570 Albrecht Feb. 7, 1937 when applied in hard Water, consisting essentially 29 2,106,240 De Groote et a1. Jan. 25, 1938 01 (a) to of a water-soluble salt of a 2,143,765 Dicke et a1 Jan,10,1939 semi-ester of an unsaturated aliphatic dicar- 2,232,485 Shipp Feb. 18, 1941 boxylic acid of the formula, 2,246,264 Pinkernelle June 17, 1941 2,343,431 Wells et a1. Mar. 7, 1944 f g E 2,417,513 Nelles Mar. 18, 1947 g j FOREIGN PATENTS 0 Number Country Date \OH 531,316 Great Britain Jan. 2, 1941 

1. A WATER-SOLUBLE COMPOSITION OF MATTER PRODUCING A SOFTENING EFFECT ON REGENERATED CELLULOSE WHEN APPLIED IN HARD WATER, CONSISTING ESSENTIALLY OF (A) 50 TO 90D% OF A WATER-SOLUBLE SALT OF A SEMI-ESTER OF AN UNSATURATED ALIPHATIC DICARBOXYLIC ACID OF THE FORMULA 